Publication Date:
2013-09-12
Description:
A series of chalcogenidoantimonates, namely [Zn(NH 3 ) 6 ](Sb III 4 S 7 ) ( 1 ), [Zn(NH 3 ) 6 ]{Zn(NH 3 ) 3 Sb V S 4 } 2 · NH 3 ( 2 ), [Mn(NH 3 ) 6 ](Sb III Se 2 ) 2 ( 3 ) and [Zn(NH 3 ) 4 ]{Zn(NH 3 )Sb III Se 3 } 2 · 3NH 3 ( 4 ) are synthesized by solvothermal technique in liquid ammonia at 50 °C from elemental zinc or manganese, antimony and sulfur or selenium. 1 (space group P ) and 2 ( P ) crystallize centrosymmetrically, whereas 3 ( Pna 2 1 ) and 4 ( P 2 1 ) represent polar structures. All compounds contain discrete cationic [Zn(NH 3 ) 4 ] 2+ , [Zn(NH 3 ) 6 ] 2+ , and [Mn(NH 3 ) 6 ] 2+ ammine complexes. In the anionic structure parts, corner-connected trigonal-pyramidal SbS 3 and SbSe 3 are the characteristic building units. 1 and 4 contain 2D polymeric anions, in the latter case with Zn 2+ cations incorporated in a selenidoantimonate(III) network. The polymeric anion in the structure of 3 is a helical chain. 2 is a molecular compound and contains dinuclear anions [S 3 Sb–S–Zn(NH 3 ) 3 ] 2– with Sb V . Raman measurements show the Sb–Ch valence vibrations in the expected region between 250–370 cm –1 for 1 and at 212 cm –1 for 4 . According to the reflectance spectrum 4 is a semiconductor with an optical band gap of 2.05(5) eV.
Print ISSN:
0044-2313
Electronic ISSN:
1521-3749
Topics:
Chemistry and Pharmacology
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